CN102626611B - Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance - Google Patents
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Abstract
The invention provides a method for preparing a metal ion imprinting adsorbent with an underwater selective recognition performance. The method comprises the steps of: preparation of an amino functional material: dispersing a nuclear body material into a methanol solution, slowly adding 3-propylaminoethoxy silane, uniformly stirring, and then, continuously adding a cross-linking agent and a stabilizer to form the amino functional material; and preparation of the metal ion imprinting adsorbent: dispersing the amino functional material in the methanol solution, and exposing to ultrasound to obtain a solution A; dissolving isonicotinic acid and metal template ions in deionized water to form a solution B; dripping the solution B into the solution A, and reacting to obtain a white sol-like product; and eluting the metal template ions: performing Soxhlet extraction by using an acetic acid-methanol solution, then eluting the metal template ions by using a hydrochloric acid, and drying to obtain the metal ion imprinting adsorbent. The metal ion imprinting adsorbent disclosed by the invention can be widely applied to advanced treatment of drinking water as well as enrichment recovery or rapid analysis detection of metal ions in different water bodies, such as industrial waste water, aquaculture water and seawater.
Description
Technical field
That the present invention relates to is the preparation method of a metal ion species trace adsorbent, belongs to environment functional material technical applications.
Background technology
Heavy metal wastewater thereby is that environmental pollution is the most serious and the mankind are endangered to maximum industrial wastewater.Heavy metal ion is of a great variety, intractability is large, stable chemical nature, be not easy to be degraded by microorganisms, by biological chain enrichment, large to vegeto-animal toxic action.Therefore, to the detection of heavy metal ions in wastewater with remove significant.
The technology that detects at present heavy metal ion mainly contains spectroscopic methodology and electrochemical process, comprising: atomic absorption spectrography (AAS), atomic emission spectrometry, atomic fluorescence method, mass spectrography etc., voltammetry, polarography, potentiometry, conductimetry etc.Spectroscopic methodology is pretreatment trouble when detecting heavy metal ion, and most nonmetalloids can not directly be measured, the range of linearity narrow (generally in a number order magnitude range) of standard working curve, and for complex sample, interference ratio is more serious, complicated operation, instrument is expensive.Electrochemical process can detect heavy metal ion in water simply, fast, yet electrochemical process is used mercury electrode easily to cause secondary pollution in testing process.
Absorption method is one of most important method for treating water, and absorption method is widely used in heavy metal containing wastewater treatment.Adsorbent kind is a lot of as active carbon, clay, flyash, peat, bark, chitin, liver moss, marine alga, rice husk etc.Wherein active carbon has special loose structure, and huge surface area and high-adsorption-capacity are to remove the most widely used adsorbent of heavy metal ion in water; Yet its non-selective, high-quality, expensively limit its use.Therefore, develop a kind of high efficiency selected absorption property that has in water, can, for detection of heavy metal ion, also can be very important for the sorbing material of removal of heavy metal ions.
Metal ion imprinted polymer refers to take metal ion as template, the polymer-function material to the selective absorption of templated metal ion that utilizes engram technology to prepare.Metal ion engram technology is a branch direction of molecular imprinting research, is the cross discipline together growing up with organic molecule engram technology.Metal ion imprinted polymer has selective height, good stability, preparation cost is low and the advantage such as applied range, is widely used in recent years at aspects such as chromatographic isolation, film separation, SPE, chiral Recognition, biomimetic sensors.Existing metal ion imprinted polymer adopts traditional organic trace synthesizing mean mostly, the function monomer using is traditional organic functions monomers such as methacrylic acid, vinyl capric acid, although the metal ion imprinted polymer that adopts traditional organic trace method to prepare has certain Selective adsorption, its adsorption capacity is low, poor and be difficult to reuse to the Selective adsorption of metal ion in the aqueous solution.Therefore, be badly in need of to improve the application that the selective recognition of metal ion imprinted polymer in the aqueous solution and adsorption capacity improve metal ion imprinted polymer.At present, there is people once to adopt traditional metal ion blotting technology, prepared metal ion imprinted polymer.As disclosed technical scheme in the publication number patent document that is CN101735417A is: adopt crosslinking technology to introduce polyacrylonitrile at silicon oxide surface, trace rare earth ion after amidoximization transforms, the rare earth ion imprinted polymer obtaining.Its metal ion imprinted polymer that clearance of metal ion is prepared than traditional organic synthesis improves, yet its building-up process is complicated, cost is high, adopt traditional function monomer metallic print ion still exist in water to templated metal ion identification difficulty, in the situation that interfering ion exists to problems such as the selection separation property of templated metal ion are not ideal enough.Therefore, need to develop and a kind ofly heavy metal ion be had that high, the synthetic cost of good selective recognition performance, adsorption capacity is low, the simple metal ion trace of building-up process absorbent preparation method in the aqueous solution.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple, cost of material is cheap, the metal form ion of trace in water is had to very high adsorption capacity and special selective recognition performance, there is good physical chemistry and mechanical stability simultaneously, in the simple water of renovation process, there is the preparation method of selective recognition performance metal ion trace adsorbent.
The object of the present invention is achieved like this:
(1) preparation of amino functional formed material: take 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution, slowly add 1～20mL 3-the third amino ethoxy silane to stir, then continuing to add the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL, is amino functional formed material by the surface modification of nucleome;
(2) preparation of metal ion trace adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min, forms uniform solution A; The isonicotinic acid and the metal form ion that by ratio, are 1: 1～10: 1 are dissolved in deionized water, and magnetic agitation reaction 2～3h, forms homogeneous solution B; Under the state stirring, solution B is slowly added dropwise in solution A, at 20～35 ℃, react 10～18h, obtain leucosol shape product; By ethanol and deionized water, leucosol shape product is washed repeatedly, then dry at 60～80 ℃;
(3) wash-out of metal form ion: the acetic acid-methanol solution that by volume ratio is 1: 1～1: 30 extracts 10～16h by the product Soxhlet of step (2), then use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL 0.1～1.0mol/L, after being dried, make metal ion trace adsorbent.
The present invention can also comprise:
1, described nucleome material is the compound of metal oxide, two kinds of metal oxides or the compound of metal oxide and carbonaceous material, and described metal oxide is SiO
2, Fe
2o
3, TiO
2, V
2o
5, Co
3o
4, NiO, ZnO, MnO
2, Fe
3o
4, CuO, Zr
2o
3, Al
2o
3, CaO, MgO or BaO, described carbonaceous material is active carbon, CNT or graphene oxide.
2, described nucleome material is that general formula is MFe
2o
4the compound of ferrospinel, two kinds of described spinel ferrite nanocrystal composition or described ferrospinel and carbonaceous material, wherein M is any one in metallic element Mn, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi or Al, and carbonaceous material is active carbon, CNT or graphene oxide.
3, described nucleome material is that general formula is MMn
2o
4ferrospinel or two kinds of described spinel ferrite nanocrystal composition, M is any one in metallic element Fe, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi, Al.
4, described nucleome material is that general formula is M
1-xn
xfe
2o
4the compound of the ferrospinel of 0 < x < 1, two kinds of described spinel ferrite nanocrystal composition or described ferrospinel and carbonaceous material wherein, M and N are the arbitrary elements in metallic element Ni, Mn, Zn, Cu, Cr, Pb, Ba or Ca, and M and N are different elements; Carbonaceous material is active carbon, CNT or graphene oxide.
5, the ion of described metal form can be the ion of following metallic element formation: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V.
6, described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw.
7, described stabilizing agent is acetic acid or oleic acid solutions.
The preferred molar ratio example of amination functional material, isonicotinic acid and metal form ion is 1: 1: 1～8: 10: 1.The preparation feedback temperature of amino functional formed material, isonicotinic acid and templated metal ion is 25～30 ℃, and the reaction time is 12～16h.
During wash-out metal form ion, first use the acetic acid-methanol solution of volume ratio 1: 7～1: 9 that above-mentioned product Soxhlet is extracted to 12～15h, then use hydrochloric acid solution wash-out templated metal ion 2～3h under magnetic agitation of 0.2～0.4mol/L of 100mL.
Adsorbent of the present invention belongs to ion selectivity enrichment and knows method for distinguishing for underwater gold: get the throwing of 0.005～0.05g metal ion trace adsorbent and join 10～100mL containing the water sample of templated metal ion 100～1000 μ mol/L, at 20～40 ℃, shake 1～5h, centrifugal rear collection supernatant, detects the wherein content of templated metal ion.
Low for the adsorbent for heavy metal adsorption capacity in prior art, in the aqueous solution adsorption selectivity poor, can not, for problems such as fast detecting, the invention provides a kind of preparation method and application thereof in water with the metal ion trace adsorbent of high efficiency selected recognition performance.Adopt the surface imprinted method combining with sol-gel technique effectively to improve trace adsorbent selective recognition performance to heavy metal ion in the aqueous solution, realized the selective absorption to heavy metal ion in the aqueous solution, effectively avoid the interference of other materials in the aqueous solution, for reclaim and detect single heavy metal from water, provide possibility.The shortcomings such as metal ion trace adsorbent prepared by the present invention has overcome that the inorganic adsorbent hydrophobicitys such as traditional active carbon are strong, poor with heavy metal ion compatibility, adsorption capacity and selective recognition poor performance, preparation technology is simple, cost of material is cheap, the metal form ion of trace in water is had to very high adsorption capacity and special selective recognition performance, have good physical chemistry and mechanical stability, renovation process is simple simultaneously.In water, can substitute traditional adsorbent or fiber material, enriching and recovering or the rapid analysis that can be widely used in metal ion in the different water bodys such as drinking water deep processing, industrial wastewater, aquaculture system and seawater detect.
Content of the present invention is to disclose a kind of metal ion trace absorbent preparation method and application thereof in water with high efficiency selected recognition performance, it is presoma that this preparation method adopts various oxide or two kinds of complex oxides or oxide and carbonaceous material compound, 3-the third amino ethoxy silane is functionalization material, has prepared amino functional formed material; Adopting amino functional formed material is that trace supporter, isonicotinic acid are that function monomer, metal ion are imprinted templates, the method that adopts sol-gel polymerization, through steps such as trace polymerisation, wash-out templates, prepared trace adsorbent metal ion in water with high selectivity absorption property.
The specific embodiment
For a more detailed description to the present invention for example below:
Embodiment 1
Take 1.2g silica dioxide granule and be dispersed in 20mL methyl alcohol, add successively wherein 3-the third amino ethoxy silane, the ethyl orthosilicate of 3mL of 20mL, the 0.1mol/L acetic acid of 10mL makes amino functional silica dioxide granule after mechanical agitation 12h.1.0g amino functional silica dioxide granule is dispersed in 20mL methanol solution, the mixed solution that adds wherein the isonicotinic acid of 3mmol and the sodium molybdate of 0.8mmol, by distilled water washing 3 times for the product obtaining, dry after centrifugation after mechanical agitation 18h.Get volume ratio and be the methyl alcohol-acetic acid solution of 1: 9 by dried product wash-out 1h, then with the hydrochloric acid solution of 100mL1mol/L, under the effect of magnetic agitation, continue wash-out imprinted templates 3h.After dry, obtain molybdenum ion trace adsorbent.
Take 0.1mol sodium molybdate and be dissolved in the sodium molybdate storing solution that is mixed with 1mol/L in 100mL water.By the sodium molybdate storing solution dilution of 1mol/L, be that 100,200,300,400,500,800,1000 μ mol/L sodium molybdates are used solution.0.01g molybdenum ion trace adsorbent is dropped into 20mL concentration and be respectively in 100,200,300,400,500,800,1000 μ mol/L sodium molybdates use liquid, centrifugal after the 3h that vibrates under room temperature.Detect molybdenum ion content in centrifuged supernatant, calculate the adsorption capacity of molybdenum ion clearance and molybdenum ion trace adsorbent, draw adsorption isotherm and calculate and learns, molybdenum ion trace adsorbent in the aqueous solution to the adsorption capacity of molybdenum ion up to 1096 μ mol/g.
Take 0.1mol sodium molybdate, copper chloride, plumbi nitras respectively solution in 100mL water, be mixed with sodium molybdate storing solution, copper chloride storing solution, the plumbi nitras storing solution of 1mol/L.By sodium molybdate storing solution, copper chloride storing solution, the dilution of plumbi nitras storing solution, it is sodium molybdate-copper chloride-plumbi nitras mixed solution of 100,200,300,400,500,800,1000 μ mol/L, 0.01g molybdenum ion trace adsorbent is dropped in the above-mentioned solution of 20mL, centrifugal after the 3h that vibrates under room temperature.Detect the content of molybdenum ion, copper ion and lead ion in centrifuged supernatant, calculate clearance and the adsorption capacity of molybdenum ion trace adsorbent to three metal ion species of molybdenum ion, copper ion and lead ion.Under same concentrations, molybdenum ion trace adsorbent is all higher more than 50% to the clearance of copper ion, lead ion than it to the clearance of molybdenum ion, at other concentration of metal ions, be wherein in the mixed solution of 100～500 μ mol/L, than it, the clearance to copper ion, lead ion is high more than 80% to the clearance of molybdenum ion for molybdenum ion trace adsorbent.Molybdenum ion trace adsorbent is respectively 1027 μ mol/L, 97.3 μ mol/L and 54.9 μ mol/L to the adsorption capacity of molybdenum ion, copper ion and lead ion.Calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find, in the situation that solution contains interfering ion, the K of molybdenum ion trace adsorbent to molybdenum ion
d=1.055, select adsorption coefficient K=21.1, relatively adsorption coefficient K
r=0.87.Known, molybdenum ion trace adsorbent has very high selective recognition performance to molybdenum ion.
Embodiment 2
0.8g ferriferrous oxide particles, 3mL oleic acid, 1.5g lauryl sodium sulfate are dispersed in the mixed liquor of 100mL ethanol and water, in solution, add APTES 5mL, in 60 ℃ of constant temperature ageing 2h.Take out solution and be placed under permanent magnet, use absolute ethanol washing three times, distilled water washing three times, puts into thermostatic drying chamber by amino functional magnetic particles of ferroferric oxide, 80 ℃ of dry 10h.Amino functional magnetic particles of ferroferric oxide is dispersed in 20mL methanol solution, add wherein the isonicotinic acid of 0.2mmol and the sodium molybdate mixed solution of 0.3mmol, by distilled water washing 3 times for the trace adsorbent obtaining, dry after centrifugation after mechanical agitation 18h.Get volume ratio and be the methyl alcohol-acetic acid solution of 1: 9 by dried trace adsorbent wash-out 14h, then with the hydrochloric acid solution of 100mL 0.5mol/L, under the effect of magnetic agitation, continue wash-out imprinted templates 3h.After dry, obtain molybdenum ion trace magnetic adsorbent.
Take 0.1mol sodium molybdate and be dissolved in the sodium molybdate storing solution that is mixed with 1mol/L in 100mL water.By the sodium molybdate storing solution dilution of 1mol/L, be that 100,200,300,400,500,800,1000 μ mol/L sodium molybdates are used solution.0.01g molybdenum ion trace adsorbent is dropped into 20mL concentration and be respectively in 100,200,300,400,500,800,1000 μ mol/L sodium molybdates use liquid, centrifugal after the 3h that vibrates under room temperature.Detect molybdenum ion content in centrifuged supernatant, calculate the adsorption capacity of molybdenum ion clearance and molybdenum ion trace magnetic adsorbent, draw adsorption isotherm and calculate and learns, molybdenum ion trace magnetic adsorbent in the aqueous solution to the adsorption capacity of molybdenum ion up to 1105 μ mol/g.
Under same concentrations, molybdenum ion trace magnetic adsorbent is all higher more than 60% to the clearance of copper ion, lead ion than it to the clearance of molybdenum ion, at other concentration of metal ions, be in the mixed solution of 100～500 μ mol/L, than it, the clearance to copper ion, lead ion is high more than 75% to the clearance of molybdenum ion for molybdenum ion trace magnetic adsorbent.By calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find, in the situation that solution contains interfering ion, the K of molybdenum ion trace magnetic adsorbent to molybdenum ion
d=1.121, select adsorption coefficient K=22.3, relatively adsorption coefficient K
r=0.91.Known, molybdenum ion trace magnetic adsorbent has very high selective recognition performance to molybdenum ion in water.
Embodiment 3
Get 0.6g silica dioxide granule and be dispersed in 20mL methyl alcohol, add successively wherein 3-the third amino ethoxy silane, the ethyl orthosilicate of 6mL, the acetic acid of the 0.1mol/L of 1.5mL of 4mL, mechanical agitation 12h makes amino functional silica dioxide granule.Amino functional silica dioxide granule is dispersed in 20mL methanol solution, add wherein the isonicotinic acid of 2mmol and the zirconyl chloride mixed solution of 0.3mmol, by distilled water washing 3 times for the trace adsorbent obtaining, dry after centrifugation after mechanical agitation 18h.Get volume ratio and be the methyl alcohol-acetic acid solution of 1: 8 by dried trace adsorbent wash-out 14h, then with the hydrochloric acid solution of 100mL 0.1mol/L, under the effect of magnetic agitation, continue wash-out imprinted templates 3h.After dry, obtain zirconium ion trace adsorbent.
Take 0.1mol zirconium nitrate and be dissolved in the zirconium nitrate storing solution that is mixed with 1mol/L in 100mL water.By the zirconium nitrate storing solution dilution of 1mol/L, be that 100,200,300,400,500,800,1000 μ mol/L zirconium nitrates are used solution.0.01g zirconium ion trace adsorbent is dropped into 20mL concentration and be respectively in 100,200,300,400,500,800,1000 μ mol/L zirconium nitrates use liquid, centrifugal after the 3h that vibrates under room temperature.Detect zirconium ion content in centrifuged supernatant, calculate the adsorption capacity of zirconium ion clearance and zirconium ion trace adsorbent, draw adsorption isotherm and calculate and learns, zirconium ion trace adsorbent in the aqueous solution to the adsorption capacity of zirconium ion up to 1086 μ mol/g.
Under same concentrations, zirconium ion trace adsorbent is all higher more than 55% to the clearance of copper ion, lead ion than it to the clearance of zirconium ion, at other concentration of metal ions, be in the mixed solution of 100～500 μ mol/L, than it, the clearance to copper ion, lead ion is high more than 75% to the clearance of zirconium ion for zirconium ion trace adsorbent.By calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find, in the situation that solution contains interfering ion, the K of zirconium ion trace adsorbent to zirconium ion
d=1.065, select adsorption coefficient K=21.5, relatively adsorption coefficient K
r=0.79.Known, zirconium ion trace adsorbent has very high selective recognition performance to zirconium ion in water.
Embodiment 4
0.2g ferriferrous oxide particles, 0.5mL oleic acid, 0.2g lauryl sodium sulfate are dispersed in 100mL ethanol and the aqueous solution.In solution, add APTES 1mL, in 60 ℃ of constant temperature ageing 5h.Take out solution and be placed under permanent magnet, use absolute ethanol washing three times, distilled water washing three times, puts into thermostatic drying chamber by the complete amino functional magnetic particles of ferroferric oxide of modification, 80 ℃ of dry 10h.Amino functional magnetic particles of ferroferric oxide is dispersed in 20mL methanol solution, the mixed potassium dichromate that adds wherein isonicotinic acid and the 0.1mmol of 0.6mmol, by distilled water washing 3 times for the trace adsorbent obtaining, dry after centrifugation after mechanical agitation 18h.Get volume ratio and be the methyl alcohol-acetic acid solution of 1: 9 by dried trace adsorbent wash-out 14h, then with the hydrochloric acid solution of 100mL 0.3mol/L, under the effect of magnetic agitation, continue wash-out imprinted templates 3h.After dry, obtain chromium ion trace magnetic adsorbent.
Take 0.1mol potassium bichromate and be dissolved in the potassium bichromate storing solution that is mixed with 1mol/L in 100mL water.By the potassium bichromate storing solution dilution of 1mol/L, be that 100,200,300,400,500,800,1000 μ mol/L potassium bichromates are used solution.0.01g chromium ion trace adsorbent is dropped into 20mL concentration and be respectively in 100,200,300,400,500,800,1000 μ mol/L potassium bichromates use liquid, centrifugal after the 3h that vibrates under room temperature.Detect content of chromium ion in centrifuged supernatant, calculate the adsorption capacity of chromium ion clearance and chromium ion trace magnetic adsorbent, draw adsorption isotherm and calculate and learns, chromium ion trace magnetic adsorbent in the aqueous solution to the adsorption capacity of chromium ion up to 1189 μ mol/g.
Under same concentrations, chromium ion trace magnetic adsorbent is all higher more than 60% to the clearance of copper ion, lead ion than it to the clearance of chromium ion, at other concentration of metal ions, be in the mixed solution of 100～500 μ mol/L, than it, the clearance to copper ion, lead ion is high more than 85% to the clearance of chromium ion for chromium ion trace magnetic adsorbent.By calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find, in the situation that solution contains interfering ion, the K of molybdenum ion trace magnetic adsorbent to molybdenum ion
d=1.098, select adsorption coefficient K=21.3, relatively adsorption coefficient K
r=0.95.Known, chromium ion trace magnetic adsorbent has very high selective recognition performance to chromium ion in water.
Embodiment 5
Get the MnFe of 0.5g
2o
4particle is dispersed in 40mL methyl alcohol, adds successively wherein 3-the third amino ethoxy silane, the ethyl orthosilicate of 1mL, the acetic acid of the 0.1mol/L of 5.0mL of 5mL, and mechanical agitation 12h makes amino functional MnFe
2o
4particle.By amino functional MnFe
2o
4uniform particles is dispersed in 20mL methanol solution, adds wherein the isonicotinic acid of 3mmol and the copper chloride mixed solution of 0.2mmol, by distilled water washing 3 times for the trace adsorbent obtaining, dry after centrifugation after mechanical agitation 18h.Get volume ratio and be the methyl alcohol-acetic acid solution of 1: 8 by dried trace adsorbent wash-out 14h, then with the hydrochloric acid solution of 100mL 0.1mol/L, under the effect of magnetic agitation, continue wash-out imprinted templates 3h.After dry, obtain copper ion trace adsorbent.
Take 0.1mol copper nitrate and be dissolved in the copper nitrate storing solution that is mixed with 1mol/L in 100mL water.By the copper nitrate storing solution dilution of 1mol/L, be that 100,200,300,400,500,800,1000 μ mol/L copper nitrates are used solution.By 0.01g copper ion trace adsorbent (MnFe
2o
4particle is core) drop into 20mL concentration and be respectively 100,200,300,400,500,800,1000 μ mol/L copper nitrates and use in liquid, centrifugal after the 3h that vibrates under room temperature.Detect content of copper ion in centrifuged supernatant, calculate the adsorption capacity of copper ion clearance and copper ion trace adsorbent, draw adsorption isotherm and calculate and learns, copper ion trace adsorbent in the aqueous solution to the adsorption capacity of copper ion up to 1086 μ mol/g.
Under same concentrations, copper ion trace adsorbent is all higher more than 55% to the clearance of zinc ion, lead ion than it to the clearance of copper ion, at other concentration of metal ions, be in the mixed solution of 100～500 μ mol/L, than it, the clearance to zinc ion, lead ion is high more than 75% to the clearance of copper ion for copper ion trace adsorbent.By calculation of distribution coefficient (K
d), select adsorption coefficient (K), adsorption coefficient (K relatively
r) find, in the situation that solution contains interfering ion, the K of copper ion trace adsorbent to copper ion
d=1.121, select adsorption coefficient K=20.5, relatively adsorption coefficient K
r=0.74.Known, copper ion trace adsorbent has very high selective recognition performance to copper ion in water.
Claims (4)
1. a preparation method in water with selective recognition performance metal ion trace adsorbent, is characterized in that comprising the steps:
(1) preparation of amino functional formed material: take 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution, slowly add 1～20mL3-the third amino ethoxy silane to stir, then continuing to add the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL, is amino functional formed material by the surface modification of nucleome; Described nucleome material is the compound of metal oxide, two kinds of metal oxides or the compound of metal oxide and carbonaceous material, and described metal oxide is SiO
2, Fe
2o
3, TiO
2, V
2o
5, Co
3o
4, NiO, ZnO, MnO
2, Fe
3o
4, CuO, Zr
2o
3, Al
2o
3, CaO, MgO or BaO, described carbonaceous material is active carbon, CNT or graphene oxide; Described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw; Described stabilizing agent is acetic acid or oleic acid solutions;
(2) preparation of metal ion trace adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min, forms uniform solution A; The isonicotinic acid that is 1:1～10:1 by molar ratio and metal form ion are dissolved in deionized water, and magnetic agitation reaction 2～3h, forms homogeneous solution B; Under the state stirring, solution B is slowly added dropwise in solution A, at 20～35 ℃, react 10～18h, obtain leucosol shape product; By ethanol and deionized water, leucosol shape product is washed repeatedly, then dry at 60～80 ℃; The ion of described metal form is the ion that following metallic element forms: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V;
(3) wash-out of metal form ion: the acetic acid-methanol solution that is 1:1～1:30 by volume ratio extracts 10～16h by the product Soxhlet of step (2), then use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL0.1～1.0mol/L, after being dried, make metal ion trace adsorbent.
2. a preparation method in water with selective recognition performance metal ion trace adsorbent, is characterized in that:
(1) preparation of amino functional formed material: take 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution, slowly add 1～20mL 3-the third amino ethoxy silane to stir, then continuing to add the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL, is amino functional formed material by the surface modification of nucleome; Described nucleome material is that general formula is MFe
2o
4the compound of ferrospinel, two kinds of described spinel ferrite nanocrystal composition or described ferrospinel and carbonaceous material, wherein M is any one in metallic element Mn, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi or Al, and carbonaceous material is active carbon, CNT or graphene oxide; Described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw; Described stabilizing agent is acetic acid or oleic acid solutions;
(2) preparation of metal ion trace adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min, forms uniform solution A; The isonicotinic acid that is 1:1～10:1 by molar ratio and metal form ion are dissolved in deionized water, and magnetic agitation reaction 2～3h, forms homogeneous solution B; Under the state stirring, solution B is slowly added dropwise in solution A, at 20～35 ℃, react 10～18h, obtain leucosol shape product; By ethanol and deionized water, leucosol shape product is washed repeatedly, then dry at 60～80 ℃; The ion of described metal form is the ion that following metallic element forms: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V;
(3) wash-out of metal form ion: the acetic acid-methanol solution that is 1:1～1:30 by volume ratio extracts 10～16h by the product Soxhlet of step (2), then use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL0.1～1.0mol/L, after being dried, make metal ion trace adsorbent.
3. a preparation method in water with selective recognition performance metal ion trace adsorbent, is characterized in that:
(1) preparation of amino functional formed material: take 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution, slowly add 1～20mL 3-the third amino ethoxy silane to stir, then continuing to add the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL, is amino functional formed material by the surface modification of nucleome; Described nucleome material is that general formula is MMn
2o
4ferrospinel or two kinds of described spinel ferrite nanocrystal composition, M is any one in metallic element Fe, Ni, Zn, Ti, Cu, Cr, Cd, Pb, Sn, Ba, Bi, Al; Described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw; Described stabilizing agent is acetic acid or oleic acid solutions;
(2) preparation of metal ion trace adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min, forms uniform solution A; The isonicotinic acid that is 1:1～10:1 by molar ratio and metal form ion are dissolved in deionized water, and magnetic agitation reaction 2～3h, forms homogeneous solution B; Under the state stirring, solution B is slowly added dropwise in solution A, at 20～35 ℃, react 10～18h, obtain leucosol shape product; By ethanol and deionized water, leucosol shape product is washed repeatedly, then dry at 60～80 ℃; The ion of described metal form is the ion that following metallic element forms: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V;
(3) wash-out of metal form ion: the acetic acid-methanol solution that is 1:1～1:30 by volume ratio extracts 10～16h by the product Soxhlet of step (2), then use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL0.1～1.0mol/L, after being dried, make metal ion trace adsorbent.
4. a preparation method in water with selective recognition performance metal ion trace adsorbent, is characterized in that:
(1) preparation of amino functional formed material: take 0.1～1.6g nucleome material and evenly spread in 5～80mL methanol solution, slowly add 1～20mL3-the third amino ethoxy silane to stir, then continuing to add the crosslinking agent of 1～20mL and the stabilizing agent of 1～20mL, is amino functional formed material by the surface modification of nucleome; Described nucleome material is that general formula is M
1-xn
xfe
2o
4the compound of the ferrospinel of 0 < x < 1, two kinds of described spinel ferrite nanocrystal composition or described ferrospinel and carbonaceous material wherein, M and N are the arbitrary elements in metallic element Ni, Mn, Zn, Cu, Cr, Pb, Ba or Ca, and M and N are different elements; Carbonaceous material is active carbon, CNT or graphene oxide; Described crosslinking agent is ethyl orthosilicate, lauryl sodium sulfate or softex kw; Described stabilizing agent is acetic acid or oleic acid solutions;
(2) preparation of metal ion trace adsorbent: the amino functional formed material of 0.1～3.0mol is dispersed in 5～100mL methanol solution, and ultrasonic 15～120min, forms uniform solution A; The isonicotinic acid that is 1:1～10:1 by molar ratio and metal form ion are dissolved in deionized water, and magnetic agitation reaction 2～3h, forms homogeneous solution B; Under the state stirring, solution B is slowly added dropwise in solution A, at 20～35 ℃, react 10～18h, obtain leucosol shape product; By ethanol and deionized water, leucosol shape product is washed repeatedly, then dry at 60～80 ℃; The ion of described metal form is the ion that following metallic element forms: Li, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, Ra, Sc, Ti, Zr, Nb, Ta, Mo, Cr, W, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sn, Pb, Cu, Ag, Au, Zn, Cd, Hg, Bi, Al, Ga, In, Ge, Sb, As, Bi, Se, Te, Po, La, Ce, Eu, U or V;
(3) wash-out of metal form ion: the acetic acid-methanol solution that is 1:1～1:30 by volume ratio extracts 10～16h by the product Soxhlet of step (2), then use hydrochloric acid solution wash-out metal form ion 1～5h under magnetic agitation of 100mL0.1～1.0mol/L, after being dried, make metal ion trace adsorbent.
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